Guiding the High-Yield Synthesis of NHC-Ligated Gold Nanoclusters by 19F NMR Spectroscopy

Abstract

Optimizing the synthesis of atomically precise metal nanoclusters by virtue of molecular tools is highly desirable but quite challenging. Herein we report how ¹⁹F NMR spectroscopy can be used to guide the high-yield synthesis of N-heterocyclic carbene (NHC)-stabilized gold nanoclusters. In spite of little difference, ¹⁹F NMR signals of fluoro-incorporated NHCs (^FNHC) are highly sensitive to the tiny change in their surrounding chemical environments with different N-substituents, metals, or anions, thus providing a convenient strategy to discriminate species in reaction mixtures. By using ¹⁹F NMR, we first disclosed that the one-pot reduction of ^FNHC-Au-X (X is halide) yields multiple compounds, including cluster compounds and also a large amount of highly stable [Au(^FNHC)₂]⁺ byproduct. The detailed quantitative ¹⁹F NMR analyses over the reductive synthesis of NHC-stabilized Au nanoclusters reveal that the formation of the di-NHC complex is deleterious to the high-yield synthesis of NHC-stabilized Au nanoclusters. With the understanding, the reaction kinetic was then slowed by controlling the reduction rate to achieve the high yield of a [Au₂₄(^FNHC)₁₄X₂H₃]³⁺ nanocluster with a unique structure. The strategy demonstrated in this work is expected to provide an effective tool to guide the high-yield synthesis of organic ligand-stabilized metal nanoclusters.